Tsuneichi fujiyama



Jan. 15, 1924. 1,481,088

T. FUJIYAMA APPARATUS FOR AND PROCESS OF' MANUFACTURING NITROGEN COMPOUNDS FROM CARBIDES Filed Dec. 12, 191.8y

F l ENToR Mw L Mu/- ATTORNEY Patented Jan. 15, 1924,

v`'iurn'rlazo"s'ra'rizs PATENT ori-1eru TSUNEICHI FUJIYAMA, 0F TOKYO, JAIAN.

i 'APPARATUS Fon am` PnocEss or MANUFACTURING NITROGEN COMPOUNDS F1101:

ennemies.Y

Application tiled December 12, 191B,

T o all wh om it may concern:

Be it known that I, TsUNEIcHl FUJIYAMA, ,a subject of the Emperor of Japan, vresiding at No.` 116 Rokuchome, Aoyama-Minamilmachi, i Akasaka-ku, Tokyo, Japan, have m'ade a certain new and luseful Invention in Apparatus for and vProcesses ofM-anufac- .turing Nitrogen Compounds from Carbides,

of which the following is-aspecificationy This invention relates to the manufacture of nitrogen compounds und the object is to provide an apparatus for'and process of `manufacturing nitrogen compounds from carbides which is simple, economical, and 5in which the manufacture of nitrogen compounds may be accomplished continuously and without the application of external heat, electrical or otherwise. A v,further object of the invention is to provide an apparatus and process of the naff' vture referred to wherein the heat required for the manufacture of nitrogen compounds isderived from the chemical reaction which takesfr place in the body of thenlaterial nnder treatment in accordance with the process Set,;forth, dr-.scribed and claimed in my Patent No. 1,126,000, granted January 26, 1915.

A further object of the invention is `to providean apparatus for and process of manufacturing nitrogen compounds at low cost and of good quality.

Other objects of the invention will ap pear more fully hereinafter.

The invention consists substantially in the construction, combination location, arrangement and mode of procedure. all as will be more fully hereina ftcr set forth, as shown in the accompanying drawing, and finally pointed outfin the appended claims.

Referring to the accompanaying drawm ig. 1 is a view in side elevation showing anI apparatus embodying my invention adapted for use in practicing the process.

Fig. 2 is a view in central vertical section of -the reaction chamber.

The same part is designated by the same reference sign wherever it occurs throughrout the several views,

In `carrying; out in v Ainvention pulverized carbide is introduced preferably without contact with the outer air, into a closed receptacle or bin, precautions being prefer- Serial No. 266,421.

ably taken to exclude atmospheric air from the interior of the bin. From the bin the pulverized carbide is delivered into a reaction chamber, to which chamber is also supplied nitrogen gas. In order to initiate the reaction the puiverized carbide after being introduced into the reaction chamber is ignited, air or oxygen being supplied for this purpose. After the ignited carbide has attained a. suitable and proper reaction temperature the supply of air or oxygen is shut oli' and fresh quantities of carbide and nitrogen gas are supplied to the reaction chamber. rl he chemical reactiog, which takes place between the carbide and the nitrogen generates heat within the body of the carbide mass,.the carbide absorbing the nitrogen, and eventually producing 4the desired nitrogen compound. The heat from this lchemical reaction `is sufficient to accomplish the production of the nitrogen compound without the necessity for applying external, electrical or other heat. By progressing the nitrogen compound produced continuously through the reaction chamber. and supplying fresh quantities of crushed carbide, the action becomes continuous, the 'fresh carbide, and nitrogen beineY ii'itroduced into ille reaction chamber at one end and the finished nitrogen compound product beina-r rcnzoved from the chamber at thc other end.

This gencraly defines the nature of the operation, and I have found that the process may be carried out in a wide variety of dif ferent forms of apparatus; In the accom` panying drawing, however, I have illus1 trate-d one forni of apparatus which is suitable and which in practice l have found etticicnt `for the purpose.

In the drawing 3 designates ,qonerallv and diagrammatically a crusher, which mai' be of the usual or any ordinary form, for crushing carbide into powdered form. From the Crusher the powdered carbide is introduced through a pipe 4., and out of Contact with the air, into a bin or receptacle 5. In practice I find it preferable to exclude ai' from the receptacle One method of accomplishing this result is to sup ly dried nitrogen gas to said receptacle, as, ihr cram ple, through pipe 6 under just sufficient pressure to exclude air from said receptacle. I do not desire. however, to be limited or esV l suitable cover or the like.

, being freely open.

restricted in this respect, as obviously the bin could also be closed at the top by a. Located within the bin or receptacle 5 is a. stirring device 7 operated by means of a. pulley 8, or otherwise, from any convenient siiree of power. By the action of the stirrer the powdered carbide is maintained at a uniform and constant level within, the bin or rece tacle 5. The' powdered carbide is delivered rom the bin or receptacle 5 into'a reaction chamber 9 in any suitable or convenient manner. A simple arrangement is shown wherein a screw conveyor indicated at d0, and driven by means of pulleys 11, or otherwise, from any convenient source of power, is emplloyed to deliver the powdered carbide into t e upper end of the reaction chamber 9.. A distributor 12 driven by means of a pulley or other connection 13 from a convenient source of power operates to` evenly distribute the owdered carbide within the reaction cham- Eer 9. Nitrogen as is also supplied to the reaction chamber t rough a supply pipe con nection 14, along with the powdered carbide, or, if preferred, the nitrogen gas may be delivered directly into the reaction chamber through a supply pipe connectionindicated in dotted lines at 15. The walls of the reaction chamber indicated at 16 are referably constructed of refractory materia and of sufficient thickness to preventthe radiation therefrom'of the heat generated within the reaction`chamber b the chemical action or reaction of the carbide and nitro en as. lf desired, and preferably, and for lgurt er pro tection against heat radiation, the reaction chamber may be lined exteriorly by sheet metal plates 17. The reaction chamber is closed at the top, the carbide and 'nitrogen gas being introduced as above explained, through such closed top. Uependin from the lower open end of the reaction c lumber is a portion 18, preferably, though not necessarily, constructed of sheet steel, through which the nitrogen compounds produced nrc progressed, [he lower end of the extension 18 Disposed below the open ond of the extciision 18 are delivery rollers lf) having spiked teeth and suitably driven, for instances through pulleys 20 from a conenient source of power. These rollers Serve not only to support the column of nitrogen compound indicated at21 but also to deliver the Sallie as the continuous operation of the ap aratus proceeds.

coated beneath the delivery rollers 19 I have shown a car 22 to receive the nitrogen compound for removal. .p

It will be observed that the exteifrsion 1S is not enclosed or surrounded and therefore is; subiccted to the cooling action f'the Outer air. The reaction chamber 9, as well as the e.\tensioi n 18,.-may be supported in any suitable or convenient manner.,Y and I have 1,4s1,oss

shown supportin means 23 for this purpose. In like manner t e receiving binor hopper 5 may be conveniently supported uponbeams 24 and extensions 25 formed o n the sides of the hopper. r

If desired, suitable peep holes 26 may be formed through the wall of the upper portion of the reaction chamber, so that the condition within such chamber may be observed. In like manner a pyrometer conventionally indicated at 27 may be inserted into the reaction chamber to indicate the degree of heat therein.

In the use of the apparatus above described, and in carrying out the process o my invention, and m order to initiate the reaction within the reaction chamber, I em- .ploy a temporary support indicated at 28, which may be retained in' place in any suitable or convenient` manner, preferably by stacking up a pile of supporting bricks beneath the same within the extension 18. The ulverized material is then charged into t e chamber 9 and upon the temporary support and ignited thereon. As the proper degree of heat is attained additional raw material is distributed evenly into the reaction chamber, thereby initiating, with the intro.- duction of nitrogen gas intoI the chamber, the chemical reaction resulting from the nitrogen being absorbed by the carbid. Y As the reaction proceeds and as the supply of carbid continues t-hep reliminary ignition which is supported by air reaching the mass through the open lower end of the' extension 18, or ox gen supplied in the same manner, the su p y of oxygen and air is arrested so that t ereafter the action proceeds continuously. As the nitrogen compound is formed the temporary supports for the Vplate or mumliiirg .are removed from the bottom perlnittn 'Elie'. plate'or member 28 to gradually deseen through the extension 18. This action continues until eventually the plate or4 member 28 reaches the lower open end of the extension 18 when said plate or memberV is removed and the mass 21 of nitrogen con poundproduct will rest upon the feed rollers 19 through the action of which the mass of product is broken up and delivered into the receiving receptacle v Obviously rollers 19 may be lengthencd or increased so iio as to fully cover the size of.y the descending.`

and cooling stack 21, and car 22 may belikewise of such size as to receive the disintegrated and cooled nitrogen gompound.

As the action proceeds the nitrogen gas introduced into the reaction' chamber is vigorously absorbed in the bed of material for ,a depth of several inches beneath the upper surface of such. hed, this depth of bed constituting the reaction zone. Within this zone intense heat is produced which is transmitted to'fthe carbide fed in from the bin 5, which absoioe the nitrogen gas gradnoV ually. In this manner the reaction is pr Iberg,thet lis, the space above the mass of material inf the Vreaction chamber, should be far below that of the reactionzone. The heat generated inthe `reaction zone, after thesiaction' isinitiated, is dueisolelyV `to the Y`-chemical reactiom'whichrtaks place and doesnot require lthe use' of electrical or other means vofjexternel'heat such as ordnq'ily employed in the Vrecesses now in general use. Y. he result o? the chemical reaction is theproduction of heat and the formation of-.cyanamides or other nitrogen compounds. The Vreaction temperatures vary with the qualit Vnndnature of the carbi e emplo 'ed and o the nitrogen gas. I have found t at -fa editable reaction temprature lies within the range of 800 C.and1200 C. In practice JI- ave Yfound that a temperature of 1150` "Cfrsecures' excellent results employing ordinary commercial carbide. Theoretically 'the `greater the pressure maintained during the reaction the quicker is the reaction completed, but the difficulty arising fromleak'age'of pressure renders the use of pressure Within the reaction chamber im- V'practical@for actual operation.V I therefore findfit Yunmaeessary to employ any greater pressure in thev reactionvchamber than such iis-may herfsufiicient to 'insure the proper.

delivery of 'nitrogen gas into the reaction v'chamber'. "Ther pressure of two or three incl'ies""d? Water is sufiicient for this purpose.Y The 'speed of reaction varies accord ing to the quality of the carbide raw material employed and of the nitrogen gas,

azud, to some extent, upon the pressure maintained in the reaction chamber, and generallyothe speed of reaction controls the quantity' and quality of the nitrogen com pound` product obtained. l have found a #suitable speed of reaction suilicicnt when lll) within a period of twentyfour hours a cyenamide product'is obtained equal in quantity to a` length of two and one-half to three feet of4 the column of such product issued or delivered from the extension 1S of theV apparatus.

In initially starting the reaction within the` reaction chamber the nitrogen gas is not introduced until after the temperature of the furnacey dueto the ignition of the carb-idc with the aidof air or oxygen has rcached'the desired degree, lVhen this tcmpeinture' is reached the ignition of the mass with a'iroroxygcn is arrested and nitrogen is introduced into the nitrogen chamber or splice above the ignited mass. Thereupon u chemical reaction takes place, the heat of which is suiiicicnt to maintain the reaction. The reaction continues resulting in the formation of the desired nitro en compound, cyanamdes, for example, a dit-ional quantities of the raw material, pulverized carbide, for example, being admin ted at the top of the reaction chamber and bein evenly distributed over the surface of tge mass contained within the reaction chamber. By continuously removing increments of the formed nitrogen compounds from the bottom of the ma and continluously applying and equally distributing fresh quantities of pulverized carbide upon and over the upper surface of the muss with continuous supply of nitrogen gas to the rcaction chamber, the operation is carried on with speed, economy und eflicicncy. thc heut generated from the chemical reuction which takes place being suiiicient without rcquirin the use of application oi external heat. he refractory lining of the reaction chamber serves to prevent suiiiciently lient radiation. As the mass of formed nitrogen compounds, for example, c 'anamidcs` progresses through the extension 18 which is not enclosed 1n a refractory or other cooling jacket or lining, it becomes sufficiently cooled so that when 'it eventually emerges from `the open end of the extension 18 and gains access to the outer air it will not become oxidized, decomposed no1- ignited.

The zone within the mass of material under treatment within which thc reaction is carried on ordinarily extends io a depth of several inches beneath the upper surface of the muss, the chemicalcombinations being completed as the mass progresses through this reaction zone. Ordinarily the fresh quantities of pulvcrzcd carbide added to the upper surface of the muss in succcssive layers encounter' theV greatest degl-ec of heat and consequently the combination therewith of the nitrogen gas supplied to the reaction chamber proceeds with great vigor and activity. As thc pulver-ized carbide is supplied over thc entire surface of the mass within the reiiction chamber in evenly distributed layers throughout` the heat of chemical combination is generated uniformly throughout the entire mass thereby resulting in the production of cy anamides of uniform quality avoiding the objection of decomposition duc to luck of uniformity of heat throughout the body of the mass, such for example, as overheating in some parts of the mass and underheatingr in other parts thereof.

Ordinarily the nitrogen gas employed should preferably be in a pure state although due to the uniformity oi action resulting from equal distribution of the can hides, cyanamides und other nitrogen compounds of excellent quality are secured even when the zitrogcn i5 not entirely purified or even byprodwt nitrogen produced at low cost, such for example, as the exhaust gus from the lead chamber of sulphur-ic acid plants is employed.

Because little or no labor is required and because of the extreme simplicity of the' process and apparatus employed nitrogen com ounds may be produce at exceedingly sma l cost. i l

Having now set forth the objects and nature of my invention and a form of means capable of carr ing saine into practical cg:- eration, what l c aim as new and use l and of my own invention, and desire to Secure by Letters Patent is,-

1. The process of making nitrogen compounds wiich consists in igniting a mass Ypf raw materials to initiate the operation, then "arresting the ignition and su plyin nitrogen gas to the mass to start a c emica reaction and supplying fresh quantities of raw material to maintain the chemical reaction, and nall removing the formed nitrogen compoun s from the bottom of the mass while continuing to sup lyntrogen gas and fresh raw material t tile top of the mass.

2. The process of making nitrogen compounds from carbides which consists in igniting a mass of pulverized carbides, then arresting the ignition and supplying nitro gen gas to the ignited mass to initiatevthe chemical combination and evenly distributing fresh quantities of ulverized carbide over the upper surface o the mass to maintain the chemical combinations and removing the formed cyanamides from the bottom of the mass. 3. The process of making nitrogen compounds from carbides' which consists in igniting a mass of pulverized carbide con.

tained in a reaction chamber, then arresting the ignition Jand supplying nitro en gas to thc heated mass to inau urate ciemical reaction in the mass to p uce cyanamides under theintluence of the heat of such reaction, and progressing the formed cyanamides through the chamber and supplying fresh quantities of pulverized carbide to the mass.

4. The process of makin; nitrogen compounds from carbides which consists in igniting n mass of pulverized carbide in the presence of an oxygen-containing atmosphere to a desired temperature, then replacing the oxygen-containing atmosphere by an atmosphere of nitrogen and continuously feeding fresh supplies of carbide and nitrogen to thereby form the nitrogen cornpounds.

5. The process of ma pounds from carbides' ulvcrizing the carbide, feeding said cardo continuously to a :onction chamber, then causing an ignition in said chamber in the presence of an atmosphere containing nitrogen comcli consists in i throu h the o n end o i. t' pe fresh materials into said reaction chamber 1 to thereby form the nitro en compounds.

6. A. furnace for'manu acturing 'ni Vn' reaction chmr compounds consistin cfa having its lower en open, means to temporari y support a mass of raw material within such chamber, means for supplying nitrogen gas and fresh quantitiesof raw material through the upper en'd of; said chamber, said temporary supgpgt gradually withdrawn to permit t "Body rmed nitrogen com. ounds` to progii'hv such chamber.V n a furnace 'for the manufacture of nitrogen compounds, a reaction chamber sa having its lower end open, delivery devices disposed below the open end of such-chamber, means for continuously supplying nitrogen* as and fresh Iiluantities of the raw materia to be treats through the Aupper end of said chamber, and means to conserve heat and to promote the chemical' combination of the raw material and niilllgen gas within said chamber.

8. In a furnace for the manuimtu of nitrogen compounds, a reaction'fphamber havin an extension, delivery', defvaces disposed elow said extension, a receiving hop-l per for the raw 'material to bo treated, means to continuously deliver the -l'aw ma.- terial from said hopper, means to evenly distribute tlie same within saidchame'r, means for supplying. nitrogen gas to' snijd chamber, and means to conserve heat and to promote the chemical combination oi the nitrogen and raw material.

9. Iny a furnace forvthe manufuicture of nitrogen compounds, a ,reactionfchamber' havin an extension, deliverygvlces dial posed elow said extension, a hopr for raw material to be treated, mem

or continuous] delivering the aw ma terial from sai hop r, n'ieanir` is' regulate the distribution o 'said materi within the reaction chamber, means for supply-l means for conserving reaction temperature., for combining the nitrogen a d raw mate- Uli llm

vno

riei, and means for promoting the cooling of seid material after leaving the reaction chamber. 11. A f uqnncc for the manufacture of nitrugen compounds, comprising e heat insuleted reaction chamber superimposed and integrally united with a heat radiatin cooling chamber of vgreater length than t e reaction chamber` said reaction chamber being closed to the excess of the outer atmos- 10 my hand on this 2nd dey of December, A. 15

TSUNEICHI FUJIYAMA. 

